Polymers of 1-monoolefins and dodecatertraenes



United States Patent 3,285,889 POLYMERS 0F l-MONOOLEFINS AND DODECATETRAENES Philip M. Arnold, Bartlesville, Okla., assignor to Phillips Petroleum Company, a corporation of Delaware No Drawing. Filed Sept. 16, 1963, Ser. No. 309,304

Claims. (Cl. 260-805) This invention relates to a process for copolymerizing 1- monoolefins with a monomer which imparts unsaturation to the resulting polymer, and to the polymers so produced. In another aspect, it relates to a process for copolymerizing ethylene, at least one other l-monolefin such as propylene, and a monomer which imparts unsaturation to the resulting polymer and renders the same sulfur-vulcanizable. In another aspect, it relates to novel copolymers of l-monoolefins and monomers which impart unsaturation to the copolymers.

Many l-monoolefins, such as ethylene and propylene, are inexpensive polymerizable monomers which are commercially available in great volumes. Such monomers can be polymerized to form polymers ranging from low molecular weight oils to high molecular weight solids. The curing or vulcanization of many of these polymers cannot be conveniently carried out in the conventional manner, for example by vulcanization with sulfur as in the case of butadiene/styrene polymers, because of the lack of ethylenic unsaturation in the polymer. Vulcanization of these polymers, such as an ethylene/ propylene copolymer, requires the use of expensive high energy radiation or organic peroxides, or requires pretreatment such as chlorosulfonation or chlorination of the polymer in order to render it suitable for curing. Such process limitations detract from the gains to be had by the unique properties possessed by the polymers, especially ethylene/propylene copolymers which are high molecular weight rubber-like substances having a high degree of resistance to weathering, sunlight and ozone.

A number of processes have been proposed for chemically modifying polymers of l-monoolefins, particularly ethylene/propylene copolymers, in order to impart some degree of unsaturation to the copolymers and make it possible to cure them with sulfur. Such modifications can be achieved by incorporating a different copolymerizable monomer, but in general such modifications have not produced the polymer in good yields and have, for example in the case of a dicyclopentadiene, required large amounts of the additional monomer to impart sufficient unsaturation and long periods for the polymer to cure.

. Accordingly, an object to this invention is to provide an improved process for the polymerization of l-monoolefins. Another object is to provide improved polymers of l-monoolefins, which polymers can be cured with sulfur. Another object is to provide an improved process for chemically modifying an ethylene/propylene polymer so as to impart some degree of unsaturation thereto and make it amenable to vulcanization with sulfur. Further objects and advantages of this invention will become aparent to those skilled in the art from the following description and accompanying claims.

Briefly, the improved process of this invention comprises copolymerizing ethylene, or ethylene and at least one other l-monolefin such as propylene, with a polydiene monomer selected from the group consisting of linear octatrienes and linear dodecatetraenes, and recovering the resulting novel polymer from the polymerization reaction mixture. Such polymerization can be carried out with any polymerization coordination catalyst known in the art, which catalyst generally comprises that obtained upon commingling a reducible metal compound, such as vanadium tetrachloride or vanadium oxytrichloride, with a reducing compound of a metal, usually aluminum, such as ethylaluminum sesquichloride. The novel polymers produced by this invention have some degree of unsaturation and can range from crystalline or plastic materials to elast-omeric materials, and they can be vulcanized with sulfur to produce polymeric products which have useful properties that make them widely applicable.

The linear octatrienes or dodecatetraenes, which are employed in this invention in the polymerization of l-mon-oolefins, are liquids and are known in the art. Representative octatrienes and dodecatetraenes which can be so employed as comonomers in this invention include:

1,3 ,7-octatriene, 1,3 ,5 -octatriene, 1,3,6-octatriene, 1,4,6-octatriene, 1,4,7-octatriene, 1,3 ,7,1 l-clodecatetraene, 1,3,6,11-dodecatetraene, 1,3 ,7,10-dodecatetraene, 1,3 ,5 ,7-dodecatetraene, 1,3 ,5 ,8 -dodecatetraene, 1,3 ,5 ,9-dodecatetraene,

IO-dode catetraene, 11-dodecatetraene, 8-do decatetraene, ,3 ,6,9-dodecatetraene,

3 ,6,10-dodecatetraene, 3 ,7, l O-dodecatetraene, ,3 ,7,9-dodecatetraene,

,6,10-dodecatetraene,

,6,1 l-dodecatetraene,

, ,7,9-dodecatetraene,

,5 ,7,10-dodecatetraene,

1,5 ,7, 1 l-do decatetraene, 1,6,8,10-dodecatetraene, and

the like, including mixtures thereof. Two comonomers of this class which have been found useful in the practice of this invention are a 1,3,7-octatriene identified as USI product 63773A and a mixture of dodectetraenes identified as USI product SOD-148A, both supplied by US. Industrial Chemicals Company. The octatrienes can be made by dimerization of butadiene, and the dodecatetraenes by trimerization of butadiene.

The l-monolefins which can be copolymerized with ethylene and any one of the above-mentioned octatrienes and dodecatetraene-s can be represented by the general formula CH =CHR, where R is an alkyl radical having 1 to 6 carbon atoms. Representative l-monoolefins which can be used as comonomers include propylene l-butene, l-pentene, l-hexene, 1-octene, 3-methyl 1 pentene, 3- methyl-l-hexene, 4-ethyl-1-hexene, 4,4-dimethy1-1-pentene, 3,3-dimethyl-1butene, S-methyl-l-hexene, 4-methyl 1- heptene, S-methyl-l-heptene, 4,4-dimethyl-1 hexene, 6- methyl-l-he-ptene, 3,4,4-trimethyl-1-pentene, and the like, including mixtures of two, three or more thereof.

The relative percentages of the polymers of this invention attributable to each of the l-monoolefin monomers and the polydiene comonomer can vary widely, with the minimum amount of the polydiene comonomer being that sufiicient to impart sulfur-curability to the polymer. Generally, the polydiene comonomer will make up from 0.5 to 20 weight percent, preferably 1 to 10 weight percent,

of the polymer. Where ethylene is the sole l-monoolefin employed with the polydiene comonomer, the former will usually make up from 80 to 99.5 weight percent of the polymer. In the case where the polydiene comonomer is copolymerized with ethylene and one or more additional l-monoolefins, the polymer will comprise 20 to 75 weight percent ethylene, 20 to 75 weight percent of the additional l-monoolefins, and 0.5 to 20 weight percent of the polydiene comonomer, and preferably with the total weight percent of the additional l-monoolefins being at least 20 weight percent of the polymer and not exceeding 15 weight percent of the polydiene in the polymer.

Any of the polymerization coordination catalysts known in the prior art can be employed in the polymerization process of this invention, such catalysts comprising 1) at least one compound of a reducible polyvalent transition metal of Groups IVA, VA, VIA, VIIA, VIII of the Periodic Table (e.g., titanium, vanadium, chromium, manganese, iron, cobalt, and nickel), said reducible compound being a halide, oxyhalide, alcoholate or acetylacetonate and (2) at least one reducing compound of a metal of Groups I, II, III, IVB and VB of the Periodic Table (e.g., lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, copper, zinc, cadmium, mercury, aluminum, tin, and antimony), which is refera'bly above hydrogen in the electromotive series, said reducing compound being an organometal compound, a metal hydride, an organometal hydride or an organometal halogen compound. (The Periodic Table referred to herein and in the claims is shown on pages 448-449 of the Handbook of'Chemistry and Physics, 34th edition, published by Chemical Rubber Publishing Co., Cleveland, Ohio.) Preferably, the metal of the reducible compound is vanadium, titanium or chromium, with vanadium trichloride, vanadium tetrachloride, vanadium oxytrichloride, vanadium oxydichloride, vanadium acetylacetonate, vanadyl acetylacetonate, titanium tetrachloride, tetrabutyl titanate, tetraisopropyl titanate, chromic chloride, chromium acetylacetonate, and chromyl acetylacetonate being examples of preferred reducible components of the coordination catalyst. Preferably, the reducing compound has the general formula R MX where R is a saturated aliphatic, saturated cycloaliphatic, or aromatic hydrocarbon radical having from 1 to 20 car bon atoms, M is a metal selected from the group consisting of lithium, sodium, potassium, magnesium, calcium, zinc, mercury, aluminum, and tin, X is a halogen selected from the group consisting of chlorine, bromine, and iodine, n is a number from 1 to 4, m is a number from to 2, and n-l-m is equal to the valence of metal M. The mole ratio of the reducing compound to the reducible compound in the catalyst system can vary widely, and generally this ratio will be in the range of 1/1 to 20/1. The total catalyst level in the reaction system can also vary widely, and generally will be 0.001 to percent by weight of the total monomers, or as expressed in terms of the amount of reducible compound, the catalyst level can be in the range of 0.25 to 40 millimoles (mmo1es.) per 100 grams of the total monoolefin charged to the reaction system. The catalyst can be premixed, i.e., the catalyst components can be admixed prior to charging to the reaction system, or the catalyst can be prepared in situ in the reaction system. These components or the premixed catalyst can be charged to the reaction system as solutions in solvents like those employed as reaction diluents for the monomers and polymer.

Representative reducible transition metal compounds which can be used in making up the coordination catalysts used in preparing the polymers of this invention include: titanium tetrachloride, titanium tetrabromide, titanium oxydichloride, tetraisopropyl titanate, titanium trichloride, tetra-n-butyl titanate, tetra-Z-ethylbutyl titanate, vanadium trichloride, vanadium tetrachloride, vanadium oxyrichloride, vanadium acetylacetonate, vanadyl acetylacetonate, tetra-n-butyl vanadate, tetraethyl vanadate, trimethyl orthovanadate, vanadium oxydichloride, vanadium dichloride, Z-ethylhexyl vanadate, vanadium dibromide, vanadium pentoxide, chromyl chloride, chromium acetylacetonate, chromyl acetylacetonate, chromium chloride, cobaltous chloride, manganese bromide, cuprous chloride, ferric bromide, molybdenum chloride, nickel chloride, and the like, including mixtures thereof.

Representative reducing compounds which can be commingled with any one of the above-named transition metal compounds to prepare the coordination catalyst used in this invention include: ethylaluminum sesquichloride, ethylaluminum sesquiiodide, n-butylalurninum sesquibromide, isopropylaluminum sesquichloride, n-hexylaluminum sesquichloride, n-decylaluminum sesquiiodide, trihexylaluminum, triethylaluminum, diethylaluminum chloride, ethylaluminum dichloride, diisobutylaluminum butoxide, triisobutylaluminum, aluminum hydride, isobutylaluminum dichloride, isobutylaluminum dibutoxide, nbutylaluminum dichloride, n-butyllithium, sodium naphthalene, diisobutylzinc, lithium aluminum tetra-n-decyl, lithium aluminum tetra-n-octy-l, amylpotassium, tetraphenyltin, diethyltin diiodide, n-butylmagnesium bromide, diphenylcalcium, di-tert-butylzinc, diethylmercury, and the like, including mixtures thereof.

Representative of the coordination catalysts which can be used in this invention are those obtained upon commingling vanadium tetrachloride and ethylaluminum sesquichloride, vanadium trichloride and ethylaluminum sesquibromide, vanadium oxytrichloride and n-butylaluminum sesquibromide, vanadium oxydichloride and isopropylalu'minum sesquichloride, vanadium acetylacetone and n-hexylaluminum sesquichloride, vanadium oxydichloride and diisobutylaluminum 'butoxide, vanadium oxytrichloride and triisobutylaluminum, vanadium oxytrichloride and aluminum hydride, vanadium dichloride and triisobutylaluminum, vanadium trichloride and isobutylaluminum dichloride, vanadium tetrachloride and isobutylaluminum dibutoxide, vanadium tetrachloride and triisobutylaluminum, vanadium tetrachloride and aluminum hydride, Z-ethylhexyl vanad ate and triisobutylaluminum, titanyl dichloride and isobutylaluminum dichloride, titanium tetrachloride and isobutylaluminum dichloride, titanium tetrachloride and lithium aluminum didodecyldichloride, titanium tetrachloride and n-decylaluminum sesquiiodide, titanium tetrachloride and sodium naphthalene, tetraisopropyl titanate and triisobutylaluminium, tetraisopropyl titanate and sodium naphthalene, cobaltous chloride and triisobutylaluminum, cobalt bromide or chloride and triisobutylaluminum, manganese bromide and triisobutylaluminum, manganese bromide and diisobutylzinc, chromium chloride and triisobutylaluminum, chromium acetylacetonate and n-heptyl-aluminimum sesquichloride, cuprous chloride and triisobutylaluminum, ferric bromide and triisobutylaluminum, molybdenum chloride and triisobutylaluminum, nickel chloride and triisobutylaluminum, vanadium oxytrichloride and diethylaluminum chloride, vanadium tetrachloride and ethylaluminum dichloride, vanadium oxydiacetylacetonate and triethyl-aluminum, trimethyl orthovanadate and trihexylaluminum, vanadium tetrachloride and trihexylaluminum, vanadium oxytrichloride and butyllithium, vanadium triacetylacetonate and diethylaluminum chloride, titanium tetrachloride and trihexylaluminum, vanadium trichloride and trihexylaluminum, titanium trichloride and trihexylaluminum titanium dichloride and trihexylaluminum, vanadium trichloride and n-butyllithium, vanadium tetrachloride and amylpotassium, vanadium oxytrichloride and sodium naphthalene, vanadium oxydichloride and diethylmagnesium, vanadium acetylacetonate and butylmagnesium bromide, vanadyl acetylacetonate and diphenyl-calcium, chromic chloride and di-tert-butylzinc, chromium acetylacetonate and diethylmercury, chromyl acetylacetonate and tetraphenyltin, titanium tetrachloride and diethyltin diiodide, tetra-n-butyl titanate and diethylmagnesium, and the like.

The polymerization reaction of this invention is carried out in the absence of materials which have a deleterious effect on the catalyst (such as oxygen, carbon dioxide and water) and in a liquid phase system using a 6 Example I Ethylene/propylene/dodecatetraene copolymers were prepared in a series of five runs employing toluene or cyclohexane as reaction diluent and using as a polymer- Solvent which will usually be a hydrocarbon or a halo 5 ization coordination catalyst ethylaluminum sesquichlogenated hydrocarbon, such as propane, butane, pentane, ride (EASC) commingled with either vanadium tetra hexane, benzene, toluene, xylene, tctrachlorethylene, chloride VCI4 or Vanadium oxytrichloride V0013. In cyclohexane, methylcyclonexane, chlorobenzene, o-dieach run, a 3/1 volume mixture of propylene and ethyl chlorobenzene, d1chloromethane, 1,l,2,2-tetrachlo roethene was prepared by charging propylene to an evacuated and the T Polymer Soluble i the bomb until the pressure reached 30 p.s.i.g. and then Solvent and usu'any W111 be present m copcentratpil of charging ethylene until the total pressure was 45 p.s.i.g. 1 to Weight percent The polylmnzanol? chmdltlons The diluent (100 ml.) was charged first to the reactor can Vary W but generally the Polymerization which was then purged with nitrogen. The dodecatetra- Fem/[lure W111 be m t range of 9 to 150 i the one was then added to the reactor, followed by the ethylreaction pressure W1ll be that sufi'icient to maintain the 15 aluminum sesquichlorideu The ethylene/propylene reactlon mlxture m the hqmd Phase, can be up to ture was then introduced from the bomb reservoir, raisor m atmospheres' polymfinzatlon ing the pressure in the polymerizationreactor to about ried out in a batch manner or a continuous fashion, much 45 Charging of the reactor was done at room like the pOlYInGllZEllIIOIl processes of the pr1or ar temperature. The polymerization reaction mixture Was lowing polymerization, the polymer Product can be f 2O agitated for 5 min., after which polymerization was inve ntlon'any recovered from the emuent, Coagulation itiated by introducing the vanadium component of the with non'solvent Such as an alcohol hke lsopropyl catalyst. Then additional ethylene/propylene mixture cohol or n'butyl R P acetone or polymer can was passed to the reactor from its reservoir to maintain a be m? by SLIIPPIPE the 50km]? with heat or a constant pressure as polymerization continued. The tem An antloxldant can be mcorperated In the polymgr during perature of polymerization increased due to the exotherrecmfery procedure such. as t f t mic reaction. Table I sets forth charge materials used amine d1 tfirt butylhydmqulilone mPhBHWPhOSPhI-E, in the runs. The dodecatetraene used in these runs was heptylated dl'phenylammei 2,2 'm l' a commercially available mixture of dodecatetraenes, 6-teIt-butY1P,heny1), and 2,lbtnmethybfirhmyl"1,2411" namely USI product 800-148A, redistilled at 80400 hydroquinolme. at 3 mm Hg.

The vulcanization or curing of the novel polymers of TABLE I this invention can be carried out using conventional sulfur vulcanization procedures (e.g., 250400 F., for 5 Run Diluent EASO V014 V001 Dodecatet 120 minutes), the amount of sulfur employed generally mmoleg 1311110195 e11e,g111s, being from 0.1 to 5 parts per 100 parts of polymer (phr.), and usually about 0.5 to 3 phr. The polymers can also 1 Toluene 0.25 0.1 0 2.5 be cured with compounds which can decompose to form fif g: 8} g 3;; free radicals such as peroxides (e.g., 0.1 to 10 ph.) like di- 5 goh iei e 8. 8 isopropyl peroxide, di-teit-butyl peroxide, dibenzolyl peryo 0 examm oxide, tert.-butyl perbenzoate, etc. The polymers can 1 also be cured with combinations of peroxide and sulfur, af g .31 E f e g with peroxide/sulfur wei ht ratio of 01/1 to /1 63 mm ermma e (S or S W1 an 150p mp y alcohol solut1on of 2,2'-meth'ylene-b1s(4-methyl-6-tert-bu- V-ulcamzatwn accelerators, accelerator activators, reintyphenol) antioxidant the amount otf antioxidant used forcing agents, extenders, plasticizers, antioxidants and being 1 phn The gun/lanepropylene/ dodecatetraene fillers, like those agents used 1n compounding natural and polymer was COaguLated in isopropyl alcohol, separated synthe tlc rubbsr, can also be P Y F1nr5 and and dried. Certain properties of the polymers from the lnfofclflg agents SuCh aS Garbo? l l Qalclum runs were determined and these are set forth in Table Cate, talc, Silica, Whltmg, and tltalllllm dlOXlde, and P II, along with the amounts of polymer products recovered. ticizers such as naphthenic and parafiinic oils, can be The numbers of the polymer sample in Table II corused in compounding the polymers of this invention. respond to the numbers of the run of Table I.

TABLE II I Total unsaturation Polymer Amt. of Propylene, Inherent Toluene sample polymer, wt. percent viscosity insolubles, gms. Mmoles ICl Wt. percent wt. percent per gm. polymer as 02H,

1. 0 0. 17 0. 476 31 1.1a 2s 1. 1 0. 13 0. 304 1. 02 47 1.1 0.11 0. 30s 1. 3a 30 2. 4 0. 1s 0. 504 42 1. 02 17 1. 0 0. 23 0. 044 1. 14. 30

Such polymers will have molecular Weights in the range of about 5000 to 1,000,000, and can be used in fabricating such rubber goods and plastic products as coatings for electrical cables, window-seals, garden hose, soles and heels, belts, coated fabrics, tires, films, coatings, containers (e.g., bottles), pipes, fibers, etc.

The objects and advantatges of this invention are illustrated in the following examples, but it should be understood that the various materials used in these examples, the conditions of operation, and other details, should not be construed to unduly limit this invention.

The dodecatetraene comonomer was incorporated in the polymer products as evidenced by the unsaturation data in Table II.

Example II Copolymers of ethylene/propylene/1,3,7-octat-riene were prepared in a series of three runs, using the procedure described in Example I. In these runs, the 1,3,7- octatriene used was USI product 63773A, redistilled at 55-57 C. at 64 mm. Hg. Table III sets forth charged materials used in the runs, and Table IV sets forth the amount of polymer products obtained and certain properties thereof, the number of the polymer sample in the latter table corresponding to the number of the run in Table III.

8 In the Formula III, 333 is the number of methyl branches per 1,000 methylene groups.

The inherent viscosities referred to in the examples were determined by placing one tenth gram of polymer TABLE III in a wire cage made from 80 mesh screen and placing Run Dfluent EASC, V01, Octadiene, the wire cage in 100 ml. of toluene contained in a widemmoles mouth, 4-ounce bottle. After standing at room temperature (approximately 25 C.) for 24 hours, the cage was l Tollaeolle 8 8-} 5 removed and the solution was filtered through a sulfur ill III IIIdoIIIIIII 0 25 012 2.5 absorption tube of grade C porosity to remove any solid particles present. The resulting solution was run through TABLE IV Total unsaturation Polymer Amt. of Propylene, Inherent Toluene sample polymer, wt. percent viscosity insolubles, gms. Mmoles I01 Wt. percent wt. percent per gm. as C2H4 0.7 0.19 0. 532 1.16 38 i1; 6:51 6135i ii I65 is The octatriene was incorporated in the polymer products a medalia-type viscometer supported in a 25 C. bath. as evidenced by the unsaturation data of Table IV. The viscometer was previously calibrated with toluene. In the foregoing examples, the procedure used to de- The relative viscosity is the ratio of the viscosity of the termine total unsaturation by iodine chloride titration polymer solution to that of toluene. The inherent viswas as follows: A 0.5-gram sample of polymer was discosity is calculated by dividing the natural logarithm solved in a 75/25 volume mixture of carbon disulfide of the relative viscosity by the weight of the soluble porand chloroform, a chloroform solution of iodine chloride tion of the original ample. of known concentration (approximately 0.09-0.10 molar) The amount of toluene isolubles referred to in the exwas added, the mixture was placed in a 25 C. bath for amples is that amount of material not dissolved after one hour to allow time for reaction, and the excess of 2 gram Sample of the polymer remains in Contact with iodine chloride was titrated with 0.05 N sodium thiosul- 5 100 milliliters f toluene at room temperature f 4 fate. The millimoles of iodine chloride that reacted with hours. The Value should be below 5 Weight percent one gram f sample Was A blank was for a rubbery polymer. Ordinarily, it is preferred to have r n 11 g ly Solvent and lodme chloflde and P the value below 25 weight percent, but for some uses pnate confection Was made h g i' (mechanical goods, mats, shoe soles, etc.) it can be In expressing total unsatumflon as Welg tpercent e higher. For uses where high resilience and low heat ene, the millimoles of lCl per gram of polymer was mult1- b d t t d b1 t h h t 1 plied by the millimole weight of ethylene (i.e., 0.028) and are lmpor an 1 eslra' e 0 ave t e uene converted to percent by multiplying the product by 100. mS1u1?1es i i In the examples, an infrared procedure was used to Various modifications and alterations of this invention determine the wt. percent propylene. A carbon tetra- I W111 befiome apparent Without departlng from the 500136 chloride Solution f the polymer containing one gram and spirit of this invention and it should be understood of polymer per 100 milliliters solvent was used. The that this invention is not to be limited unduly to that solution was placed in a lSOO-micron cell and scanned for set forth herein for illustrative purposes. a peak at the 7.25 micron band using a commercial in- I claim: [frafed spectfophoiometel The number of methyl groups 1. A copolymer composition consisting essentially of Obtained from formula! 80 to 99.5 weight percent of ethylene and 0.5 to 20 Q (14,000)(A )(1,0O0) weight percent of dodecatetraene.

N gx x (I) 2. A rubbery terpolymer composition consisting esl4ooozmoiecuiar Weight of 1,000 methylene groups sentially of 20 to 75 weight percent ethylene, 20 to 75 Aq'z5zkabsorbance at the 725 micron band weight percent propylene and 0.5 to 20 weight percent of C :concentration of polymer solution in lgram/ liter dodecatetraenei 13:66 thickness in centimeters 3. In a process for forming rubbery polymer composi- =Spcific extinction fl'i i t tions, said compositions being selected from11 the group consisting of a copo ymer consisting essentia y of 80 to The .specl'fic. extmctlon coefficlent (ezzgmo) was de- 99.5 weight percent of ethylene and 0.5 to 20 weight pertermmed using three samples of an ethylene/propylene copoilymer of known propylene content as a reference cent of dodecatetraene, and terpolymers consisting esmaterial. The value was obtained by solving the equaserltlauy of 20 to 75 Welght Percent Qthylenm 20 to 75 tion weight percent of a l-monoolefin having the formula 6 7 .25) H :C

d d i f Polymer l ti i d t wherein R is selected from the group consisting of an ()9) alkyl having 1 to 6 carbon atoms and 0.5 to 20 weigh-t t=thickness of absorbing layer of polymer in centimeters percent of dodecatetraene, said process comprising the N number of methyl branches in control polymer The percent propylene was calculated as follows:

step of polymerizing a monomer selected from the group consisting of ethylene and mixtures of ethylene and at least one of said 1-rnonoolefins in the presence of a coordination catalyst obtained upon commingling ethylalurninum sesquichloride with a component selected from 9 19 the group consisting of vanadium tetrachloride and vana- References Cited by the Examiner dium o xytrichloride, at a temperature ranging from 80 UNITED STATES PATENTS to 150 C. and a pressure ranglng from 1 to 500 atmospheres, in the presence of either a toluene or cyclohexane 3:480 4/1960 Gresham et a1 diluent; incorporating into the polymerization system 5 2,962,490 11/1960 Edmonds et 260 88-2 dodecatetraene in an amount as stated hereinabove to 3,058,963 10/1962 Vandenbellg 260;93-7

make the resulting copolymer or terpolymer amenable to vulcanization with sulfur and recovering the copoly- JOSEPH SCHOFER Pmmry Examme mer or terpoiymer from the polymerization system. W. HOOVER, Assistant Examiner. 

3. IN A PROCESS FOR FORMING RUBBERY POLYMER COMPOSITIONS, SAID COMPOSITIONS BEING SELECTED FROM THE GROUP CONSISTING OF A COPOLYMER CONSISTING ESSENTIALLY OF 80 TO 99.5 WEIGHT PERCENT OF ETHYLENE AND 0.5 TO 20 WEIGHT PERCENT OF DODECATETRAENE, AND TERPOLYMERS CONSISTING ESSENTIALLY OF 20 TO 75 WEIGHT PERCENT ETHYLENE, 20 TO 75 WEIGHT PERCENT OF A 1-MONOOLEFIN HAVING THE FORMULA 